The present invention is directed to olefin polymers, such as polyethylene, polypropylene, and copolymers of ethylene and propylene, and to the preparation of such olefin polymers. These polymers include homopolymers of olefins, as well as copolymers of different olefins. The present invention is also directed to processes of making these olefin polymers, which typically use a transition metal complex, in which the transition metal is a Group 8-10 metal, as the polymerization catalyst. The polymers have a wide variety of applications, including use as packaging materials and adhesives. In addition, the present invention is directed to catalysts for the polymerization of olefins.
Olefin polymers are used in a wide variety of products, from sheathing for wire and cable to film. Olefin polymers are used, for instance, in injection or compression molding applications, in extruded films or sheeting, as extrusion coatings on paper, for example photographic paper and digital recording paper, and the like. Improvements in catalysts have made it possible to better control polymerization processes, and, thus, influence the properties of the bulk material. Increasingly, efforts are being made to tune the physical properties of plastics for lightness, strength, resistance to corrosion, permeability, optical properties, and the like, for particular uses. Chain length, polymer branching and functionality have a significant impact on the physical properties of the polymer. Accordingly, novel catalysts are constantly being sought in attempts to obtain a catalytic process which permits more efficient and better controlled polymerization of olefins.
Conventional polyolefins are prepared by a variety of polymerization techniques, including homogeneous and heterogeneous polymerizations. Certain transition metal catalysts, such as those based on titanium compounds (e.g., TiCl3 or TiCl4) in combination with organoaluminum cocatalysts, are used to make linear and linear low density polyethylenes as well as poly-xcex1-olefins such as polypropylene. These so-called xe2x80x9cZiegler-Nattaxe2x80x9d catalysts are quite sensitive to oxygen and are ineffective for the copolymerization of nonpolar and polar monomers.
Recent advances in non-Ziegler-Natta olefin polymerization catalysis include the following:
L. K. Johnson et al., WO Patent Application 96/23010, disclose the polymerization of olefins using cationic nickel, palladium, iron, and cobalt complexes containing diimine and bisoxazoline ligands. This document also describes the polymerization of ethylene, acyclic olefins, and/or selected cyclic olefins and optionally selected unsaturated acids or esters such as acrylic acid or alkyl acrylates to provide olefin homopolymers or copolymers.
European Patent Application No. 381,495 describes the polymerization of olefins using palladium and nickel catalysts which contain selected bidentate phosphorous containing ligands.
L. K. Johnson et al., J. Am. Chem. Soc., 1995, 117, 6414, describe the polymerization of olefins such as ethylene, propylene, and 1-hexene using cationic xcex1-diimine-based nickel and palladium complexes. These catalysts have been described to polymerize ethylene to high molecular weight branched polyethylene. In addition to ethylene, Pd complexes act as catalysts for the polymerization and copolymerization of olefins and methyl acrylate.
G. F. Schmidt et al., J. Am. Chem. Soc., 1985, 107, 1443, describe a cobalt(III) cyclopentadienyl catalytic system having the structure [C5Me5(L)CoCH2CH2xe2x80x94xcexcxe2x80x94H]+, which provides for the xe2x80x9clivingxe2x80x9d polymerization of ethylene.
M. Brookhart et al., Macromolecules, 1995, 28, 5378, disclose using such xe2x80x9clivingxe2x80x9d catalysts in the synthesis of end-functionalized polyethylene homopolymers.
U. Klabunde, U.S. Pat. Nos. 4,906,754, 4,716,205, 5,030,606, and 5,175,326, describes the conversion of ethylene to polyethylene using anionic phosphorous/oxygen donors ligated to Ni(II). The polymerization reactions were run between 25 and 100xc2x0 C. with modest yields, producing linear polyethylene having a weight-average molecular weight ranging between 8K and 350K. In addition, Klabunde describes the preparation of copolymers of ethylene and functional group containing monomers.
M. Peuckert et al., Organomet., 1983, 2(5), 594, disclose the oligomerization of ethylene using phosphine/carboxylate donors ligated to Ni(II), which showed modest catalytic activity (0.14 to 1.83 TO/s). The oligomerizations were carried out at 60 to 95xc2x0 C. and 10 to 80 bar ethylene in toluene, to produce linear xcex1-olefins.
R. E. Murray, U.S. Pat. Nos. 4,689,437 and 4,716,138, describes the oligomerization of ethylene using phosphine/sulfonate donors ligated to Ni(II). These complexes show catalyst activities approximately 15 times greater than those reported with phosphine/carboxylate analogs.
W. Keim et al., Angew. Chem. Int. Ed. Eng., 1981, 20, 116, and V. M. Mohring et al., Angew. Chem. Int. Ed. Eng., 1985, 24, 1001, disclose the polymerization of ethylene and the oligomerization of xcex1-olefins with aminobis(imino)phosphorane nickel catalysts.
G. Wilke, Angew. Chem. Int. Ed. Engl., 1988, 27, 185, describes a nickel allyl phosphine complex for the polymerization of ethylene.
K. A. O. Starzewski et al., Angew. Chem. Int. Ed. Engl., 1987, 26, 63, and U.S. Pat. No. 4,691,036, describe a series of bis(ylide) nickel complexes, used to polymerize ethylene to provide high molecular weight linear polyethylene.
WO Patent Application 97/02298 discloses the polymerization of olefins using a variety of neutral N, O, P, or S donor ligands, in combination with a nickel(0) compound and an acid.
Brown et al., WO 97/17380, describes the use of Pd xcex1-diimine catalysts for the polymerization of olefins including ethylene in the presence of air and moisture.
Fink et al., U.S. Pat. No. 4,724,273, have described the polymerization of xcex1-olefins using aminobis(imino)phosphorane nickel catalysts and the compositions of the resulting poly(xcex1-olefins).
Additional recent developments are described by Sugimura et al., in JP 96-84344, JP 96-84343, and WO 9738024, and by Yorisue et al., in JP 96-70332. Moreover, the University of North Carolina and Du Pont have reported the polymerization of olefins using neutral nickel catalysts in WO 9830609 and WO 9830610.
Notwithstanding these advances in non-Ziegler-Natta catalysis, there remains a need for efficient and effective Group 8-10 transition metal catalysts for effecting polymerization of olefins. In addition, there is a need for novel methods of polymerizing olefins employing such effective Group 8-10 transition metal catalysts. In particular, there remains a need for Group 8-10 transition metal olefin polymerization catalysts with both improved temperature stability and functional group compatibility. Further, there remains a need for a method of polymerizing olefins utilizing effective Group 8-10 transition metal catalysts in combination with a Lewis acid so as to obtain a catalyst that is more active and more selective.
The present invention provides a process for the production of polyolefins, comprising: contacting, at a temperature from about xe2x88x92100xc2x0 C. to about 200xc2x0 C., one or more monomers of the formula RCHxe2x95x90CHR3 with a catalyst comprising (i) a transition metal complex of formula I or Ia, and, optionally, (ii) a neutral Lewis acid; 
wherein R and R3 are each, independently, hydrogen, hydrocarbyl or substituted hydrocarbyl and may be linked to form a cyclic olefin;
R1 and R2 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl;
Q is (i) Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH2) or S(O)(OH);
L is a monoolefin or a neutral Lewis base that can be displaced by a monoolefin;
T is hydrogen, hydrocarbyl or substituted hydrocarbyl, or may be taken together with L to form a xcfx80-allyl group; and
M is Ni(II), Pd(II), Co(II) or Fe(II). The catalyst may be in supported or unsupported form.
This invention also provides a compound of formula I or Ia: 
wherein R1 and R2 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl;
Q is (i) Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH2) or S(O)(OH);
L is a monoolefin or a neutral Lewis base that can be displaced by a monoolefin;
T is hydrogen, hydrocarbyl or substituted hydrocarbyl, or may be taken together with L to form a xcfx80-allyl group; and
M is Ni(II), Pd(II), Co(II) or Fe(II).
This invention also provides a catalyst composition which comprises (i) a compound of formula I or Ia, and optionally, (ii) a neutral Lewis acid; 
wherein R1 and R2 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl;
Q is (i) Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH2) or S(O)(OH);
L is a monoolefin or a neutral Lewis base that can be displaced by a monoolefin;
T is hydrogen, hydrocarbyl or substituted hydrocarbyl, or may be taken together with L to form a xcfx80-allyl group; and
M is Ni(II), Pd(II), Co(II) or Fe(II). The catalyst may be in supported or unsupported form.
The present invention further relates to process for the preparation of a supported catalyst, comprising: contacting (i) a compound of formula I or Ia, (ii) silica, and (iii) a neutral Lewis acid selected from the group consisting of B(C6F5)3, methylaluminoxane, BPh3, and B(3,5-(CF3)C6H3)3; 
wherein R1 and R2 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl;
Q is (i) Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH2) or S(O)(OH);
L is a monoolefin or a neutral Lewis base that can be displaced by a monoolefin;
T is hydrogen, hydrocarbyl or substituted hydrocarbyl, or may be taken together with L to form a xcfx80-allyl group; and
M is Ni(II), Pd(II), Co(II) or Fe(II).
The present invention also provides a process for the polymerization of olefins, comprising: contacting, at a temperature from about xe2x88x92100xc2x0 C. to about 200xc2x0 C., one or more monomers of the formula RCHxe2x95x90CHR3 with a catalyst comprising the reaction product of (i) a compound of the formula II, or tautomers thereof, (ii) a suitable precursor selected from the group consisting of Ni, Pd, Co, and Fe compounds, and, optionally, (iii) a neutral Lewis acid; 
wherein R and R3 are each, independently, hydrogen, hydrocarbyl or fluoroalkyl and may be linked to form a cyclic olefin;
R1 and R2 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl; and
Q is (i) Cxe2x80x94R4 wherein R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2 or (iii) S(NH)(NH2) or S(O)(OH). The catalyst may be in supported or unsupported form.
The invention also provides a compound of formula II, or tautomers thereof: 
wherein R1 and R2 are both sterically hindered aryl rings; and
Q is (i) Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH) or S(O)(OH).
The present invention further provides a catalyst composition which comprises the reaction product of (i) a compound of formula II, or tautomers thereof, (ii) a suitable precursor selected from the group consisting of Ni, Pd, Co, and Fe compounds, and, optionally, (iii) a neutral Lewis acid; 
wherein R1 and R2 are both sterically hindered aryl rings; and
Q is (i) Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH2) or S(O)(OH). The catalyst may be in supported or unsupported form.
The invention further provides a process for the preparation of a supported catalyst, comprising: contacting (i) a compound of the formula II, or tautomers thereof, (ii) a suitable precursor selected from the group consisting of Ni, Pd, Co, and Fe compounds, (iii) a neutral Lewis acid selected from the group consisting of B(C6F5)3, methylaluminoxane, BPh3, and B(3,5-(CF3)C6H3)3, and (iv) silica; 
wherein R and R3 are each, independently, hydrogen, hydrocarbyl or fluoroalkyl and may be linked to form a cyclic olefin;
R1 and R2 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl; and
Q is (i) Cxe2x80x94R4, wherein R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH2) or S(O)(OH).
The present invention also provides a process for the polymerization of olefins, comprising: contacting one or more monomers of the formula RCHxe2x95x90CHR3 with a catalyst comprising the reaction product of (i) a binucleating or multinucleating ligand complexed to a Group 8-10 transition metal M and (ii) one or more neutral Lewis acids, wherein the Lewis acid or acids are bound to one or more heteroatoms which are xcfx80-conjugated to the donor atom or atoms bound to the transition metal M; and wherein R and R3 each, independently, represent a hydrogen, a hydrocarbyl, a fluoroalkyl, or may be linked to form a cyclic olefin. The catalyst may be in supported or unsupported form.
The invention also provides a catalyst composition comprising the reaction product of (i) a Group 8-10 transition metal M, (ii) one or more neutral Lewis acids, and (iii) a binucleating or multinucleating compound of the formula II: 
wherein the Lewis acid or acids are bound to one or more heteroatoms which are xcfx80-conjugated to the donor atom or atoms bound to the transition metal M;
R1 and R2 are both sterically hindered aryl rings; and
Q is (i) Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH2) or S(O)(OH). The catalyst may be in supported or unsupported form.
The invention further provides a process for the polymerization of olefins, comprising: contacting, at a temperature from about xe2x88x92100xc2x0 C. to about 200xc2x0 C., one or more monomers of the formula RCHxe2x95x90CHR3, with a catalyst comprising the reaction product of (i) an anionic compound of the formula III, (ii) a suitable divalent metal precursor selected from the group consisting of Ni(II), Pd(II), Co(II), and Fe(II) compounds, and, optionally, (iii) a neutral Lewis acid; 
wherein R and R3 are each, independently, hydrogen, hydrocarbyl or fluoroalkyl and may be linked to form a cyclic olefin;
R1 and R2 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl; and
Q is Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or Oxe2x80x94Si(tert-butyl)(CH3)2. The catalyst may be in supported or unsupported form.
The present invention also provides a process for the production of polyolefins, comprising: contacting, at a temperature from about xe2x88x92100xc2x0 C. to about 200xc2x0 C., one or more monomers of the formula RCHxe2x95x90CHR3 with a catalyst comprising (i) a transition metal complex of formula V or Va, or tautomers thereof, and, optionally, (ii) a neutral Lewis acid; 
wherein R and R3 are each, independently, hydrogen, hydrocarbyl or substituted hydrocarbyl and may be linked to form a cyclic olefin;
R1 and R2 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl;
Q is (i) Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH2) or S(O)(OH);
L is a monoolefin or a neutral Lewis base that can be displaced by a monoolefin;
T is hydrogen, hydrocarbyl or substituted hydrocarbyl, or may be taken together with L to form a xcfx80-allyl group;
M is Ni(II), Pd(II), Co(II) or Fe(II);
R10 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl; and
X is a weakly coordinating anion. The catalyst may be in supported or unsupported form.
The invention further provides a compound of formula V or Va, or tautomers thereof: 
R1 and R2 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl;
Q is (i) Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH2) or S(O)(OH);
L is a monoolefin or a neutral Lewis base that can be displaced by a monoolefin;
T is hydrogen, hydrocarbyl or substituted hydrocarbyl, or may be taken together with L to form a xcfx80-allyl group;
M is Ni(II), Pd(II), Co(II) or Fe(II);
R10 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl; and
X is a weakly coordinating anion.
The present invention also provides a catalyst composition which comprises (i) a transition metal complex of formula V or Va, or tautomers thereof, and, optionally, (ii) a neutral Lewis acid; 
R1 and R2 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl;
Q is (i) Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH) or S(O)(OH);
L is a monoolefin or a neutral Lewis base that can be displaced by a monoolefin;
T is hydrogen, hydrocarbyl or substituted hydrocarbyl, or may be taken together with L to form a xcfx80-allyl group;
M is Ni(II), Pd(II), Co(II) or Fe(II);
R10 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl; and
X is a weakly coordinating anion. The catalyst may be in supported or unsupported form.
The invention further provides a process for the production of polyolefins, comprising: contacting, at a temperature from about xe2x88x92100xc2x0 C. to about 200xc2x0 C., one or more monomers of the formula RCHxe2x95x90CHR3 with a catalyst comprising (i) a transition metal complex of formula VI or VIa, and (ii) a neutral Lewis acid; 
wherein R and R3 are each, independently, hydrogen, hydrocarbyl or substituted hydrocarbyl and may be linked to form a cyclic olefin;
R1 and R2 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl;
Q is (i) Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH2) or S(O)(OH);
Z and W each independently represent Cl, Br, I, methyl, or H;
M is Ni(II), Pd(II), Co(II) or Fe(II); and
R10 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl. The catalyst may be in supported or unsupported form.
The present invention also provides a compound of formula VI or VIa: 
R1 and R2 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl;
Q is (i) Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH2) or S(O)(OH);
Z and W each independently represent Cl, Br, I, methyl, or H;
M is Ni(II), Pd(II), Co(ID or Fe(II); and
R10 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl.
Finally, the present invention provides a catalyst composition which comprises (i) a transition metal complex of formula VI or VIa, and (ii) a neutral Lewis acid; 
R1 and R2 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl;
Q is (i) Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH2) or S(O)(OH);
Z and W each independently represent Cl, Br, I, methyl, or H;
M is Ni(II), Pd(n), Co(II) or Fe(II); and
R10 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl. The catalyst may be in supported or unsupported form.
In this disclosure, certain chemical groups and compounds are described by certain terms, symbols, and formulas. No specific stereochemistry is implied or intended by the formulas. Symbols ordinarily used to denote elements in the Periodic Table take their ordinary meaning, unless otherwise specified. The terms are defined as follows:
Examples of neutral Lewis bases include, but are not limited to, (i) ethers, for example, diethyl ether or tetrahydrofuran, (ii) organic nitriles, for example, acetonitrile, (iii) organic sulfides, for example, dimethylsulfide, or (iv) monoolefins, for example, ethylene, hexene or cyclopentene.
Examples of neutral Lewis acids include, but are not limited to, methylaluminoxane (hereinafter xe2x80x9cMAOxe2x80x9d) and other aluminum sesquioxides, R73Al, R72AlCl, R7AlCl2 (where R7 is alkyl), organoboron compounds, boron halides, B(C6F5)3, BPh3, and B(3,5-(CF3)C6H3)3.
Examples of ionic compounds comprising a cationic Lewis acid include: R93Sn[BF4] (where R9 is hydrocarbyl), MgCl2, and H+Xxe2x88x92, where Xxe2x88x92 is a weakly coordinating anion.
The term xe2x80x9cweakly coordinating anionxe2x80x9d is well known in the art and generally refers to a large bulky anion capable of delocalization of the negative charge of the anion. Suitable weakly coordinating anions include, but are not limited to, PF6xe2x88x92, BF4xe2x88x92, SbF6xe2x88x92, (Ph)4Bxe2x88x92 wherein Ph=phenyl, and xe2x88x92BAr4 wherein xe2x88x92BAr4=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. The coordinating ability of such anions is known and described in the literature (e.g., S. Strauss et al., Chem. Rev., 1993, 93, 927).
A xe2x80x9csterically hindered arylxe2x80x9d means (i) a phenyl ring with hydrocarbyl, substituted hydrocarbyl, F, Cl, Br or silyl substituents at both the 2- and 6-positions, optionally substituted elsewhere with hydrocarbyl, substituted hydrocarbyl, F, Cl, Br, silyl, hydroxy, methoxy, nitro, cyano, phenylsulfonyl, CO2Me, CO2H, C(O)CH3, CF3, or fluoroalkyl substituents, (ii) a 2-substituted napth-1-yl ring, optionally substituted elsewhere with hydrocarbyl, substituted hydrocarbyl, F, Cl, Br, silyl, hydroxy, methoxy, nitro, cyano, phenylsulfonyl, CO2Me, CO2H, C(O)CH3, CF3, or fluoroalkyl substituents, (iii) a 9-anthracenyl or a 1,2,3,4,5,6,7,8-octahydro-9-anthracenyl ring, optionally substituted elsewhere with hydrocarbyl, substituted hydrocarbyl, F, Cl, Br, silyl, hydroxy, methoxy, nitro, cyano, phenylsulfonyl, CO2Me, CO2H, C(O)CH3, CF3, or fluoroalkyl substituents, or (iv) an aromatic substituted hydrocarbyl with steric properties functionally equivalent (in the context of this invention) to one or more of the following sterically hindered aryls: 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, 2,6-dimethyl-4-nitrophenyl, 2,6-dimethyl-4-phenylsulfonylphenyl, 2-isopropyl-6-methylphenyl, 2,6-bis(trifluoromethyl)phenyl, 2,6-dimethyl-4-methoxyphenyl, 2-methylnapth-1-yl, 9-anthracenyl, 1,2,3,4,5,6,7,8-octahydro-9-anthracenyl, 2,6-diclorophenyl, 2,6-dibromophenyl, 2-tert-butyl-6-methylphenyl, 2-trimethylsilylnapth-1-yl, 2-chloro-6-methylphenyl, 4-cyano-2,6-dimethylphenyl, 2,6-diisopropyl-4-methoxyphenyl, 2,4,6-tri-tert-butylphenyl, 2-chloro-6-tert-butylphenyl, 2-tert-butylphenyl, and 2-trimethylsilylphenyl.
A xe2x80x9chydrocarbylxe2x80x9d group means a linear, branched or cyclic group which contains only carbon and hydrogen atoms. Examples include: C1-C20 alkyl; C1-C20 alkyl substituted with one or more groups selected from C1-C20 alkyl C3-C8 cycloalkyl or aryl; C3-C8 cycloalkyl; C3-C8 cycloalkyl substituted with one or more groups selected from C1-C20 alkyl, C3-C8 cycloalkyl or aryl; C6-C14 aryl; and C6-C14 aryl substituted with one or more groups selected from C1-C20 alkyl, C3-C8 cycloalkyl or aryl; where the term xe2x80x9carylxe2x80x9d preferably denotes a phenyl, napthyl, or anthracenyl group.
Examples of groups useful as the group Q include (i) C-aryl, where aryl is phenyl, pentafluorophenyl, or phenyl substituted with F, Cl, Br, methoxy, cyano, nitro, CO2H, CF3, fluoroalkyl, or phenylsulfonyl, (ii) C-tert-butyl, Cxe2x80x94CF3, or C-fluoroalkyl, (iii) Cxe2x80x94Sxe2x80x94R5 or Cxe2x80x94Oxe2x80x94R5, where R5 is C1-C20 alkyl, silyl, phenyl, or phenyl substituted with F, Cl, Br, CF3, fluoroalkyl, CO2H, methoxy, cyano, nitro, or phenylsulfonyl, (iv) C-silyl, (v) P(NH2)2, or (vi) S(NH)(NH2) or S(O)(OH).
A xe2x80x9csilylxe2x80x9d group refers to a SiR63 group where Si is silicon and R6 is hydrocarbyl or substituted hydrocarbyl or silyl, as in Si(SiR63)3.
A xe2x80x9cheteroatomxe2x80x9d refers to an atom other than carbon or hydrogen. Preferred heteroatoms include oxygen, nitrogen, phosphorus, sulfur, selenium, silicon, arsenic, chlorine, bromine, and fluorine.
A xe2x80x9cfluoroalkylxe2x80x9d as used herein refers to a C1-C20 alkyl group substituted by one or more fluorine atoms.
A xe2x80x9csubstituted hydrocarbylxe2x80x9d refers to a hydrocarbyl substituted with one or more heteroatoms. Examples include: 2,6-dimethyl-4-methoxyphenyl, 2,6-diisopropyl-4-methoxyphenyl, 4-cyano-2,6-dimethylphenyl, 2,6-dimethyl-4-nitrophenyl, 2,6-difluorophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl, 4-methoxycarbonyl-2,6-dimethylphenyl, 2-tert-butyl-6-chlorophenyl, 2,6-dimethyl-4-phenylsulfonylphenyl, 2,6-dimethyl-4-trifluoromethylphenyl, 2,6-methyl-4-hydroxyphenyl, 9-hydroxyanthr-10-yl, 2-chloronapth-1-yl, 4-methoxyphenyl, 4-nitrophenyl, 9-nitroanthr-10-yl, CH2OCH3, cyano, trifluoromethyl, or fluoroalkyl.
A xe2x80x9cheteroatom connected hydrocarbylxe2x80x9d refers to a group of the type Z-(hydrocarbyl), where Z is a divalent heteroatom, preferably O or S, or Z-(hydrocarbyl)2, where Z is a trivalent heteroatom, preferably N. Examples include: OCH3, OPh, N(CH3)2, SCH3, or SPh.
A xe2x80x9cheteroatom connected substituted hydrocarbylxe2x80x9d refers to a group of the type Z-(substituted hydrocarbyl), where Z is a divalent heteroatom, preferably O or S, or Z-(substituted hydrocarbyl)2, where Z is a trivalent heteroatom, preferably N. Examples include: OCH2CF3, SC(O)CH3, and 1-morpholinyl.
A xe2x80x9cmono-olefinxe2x80x9d refers to a hydrocarbon containing one carbonxe2x80x94carbon double bond.
A xe2x80x9csuitable precursorxe2x80x9d refers to a zerovalent or divalent transition metal compound which may be combined with compound H, and optionally a neutral Lewis acid, to form an active olefin polymerization catalyst. Examples of suitable precursors include: bis(1,5-cyclooctadiene)nickel(0) and bis[(1,2, 3-xcex73-2-propenyl)nickel(II)].
A xe2x80x9csuitable divalent metal precursorxe2x80x9d refers to a divalent transition metal compound which may be combined with compound III, and optionally a neutral Lewis acid, to form an active olefin polymerization catalyst. Examples include: (1,2-dimethoxyethane)nickel(II) dibromide, bis[(xcexc-chloro)(1, 2, 3-xcex73-2-propenyl)nickel(II)], bis[(xcexc-chloro)(1, 2, 3-xcex73-2-propenyl)palladium(II)], bis[(xcexc-chloro)(1, 2, 3-xcex73-1-trimethylsilyloxy-2-propenyl)nickel(II)], CoBr2, FeBr2.
A xe2x80x9cxcfx80-allylxe2x80x9d group refers to a monoanionic group with three sp2 carbon atoms bound to a metal center in a xcex73-fashion. Any of the three sp2 carbon atoms may be substituted with a hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or O-silyl group. Examples of xcfx80-allyl groups include: 
The term xe2x80x9cpolymerxe2x80x9d as used herein is meant a species comprised of monomer units and having a degree of polymerization (DP) of ten or higher.
As used herein, the terms xe2x80x9cmonomerxe2x80x9d and xe2x80x9colefin monomerxe2x80x9d refer to the olefin or other monomer compound before it has been polymerized; the term xe2x80x9cmonomer unitsxe2x80x9d refers to the moieties of a polymer that correspond to the monomers after they have been polymerized.
Described herein is a process for the polymerization of olefins. Preferred olefins include ethylene and xcex1-olefins such as propylene, 1-butene, 1-hexene, 1-octene, and cyclic olefins such as cyclopentene.
When the polymerizations are conducted in the liquid phase, the liquid phase may include solvent or neat monomer. The molar ratio of neutral Lewis acid to transition metal complex can be from 0 to 10000, preferably 0 to 100, more preferably 0 to 10. The pressure at which the ethylene polymerizations and copolymerizations take place can be from 1 atmosphere to 1000 atmospheres, preferably 1 to 100 atmospheres.
While not wishing to be bound by theory, the present inventors believe that the neutral Lewis acid may be acting to further activate the catalysts disclosed herein via coordination to one or more of those heteroatoms which are not directly bound to the transition metal M, but which are xcfx80-conjugated to the nitrogens which are bound to the transition metal M. Substituents which contain additional Lewis basic groups, including, but not limited to, methoxy groups, positioned so as to further promote the binding of the Lewis acid at such xcfx80-conjugated heteroatoms, are also included in this invention. A non-limiting example of secondary Lewis acid binding would include formula IV or IVa as follows: 
wherein R1 and R2 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl;
Q is (i) Cxe2x80x94R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl, (ii) P(NH2)2, or (iii) S(NH)(NH2) or S(O)(OH);
L is a monoolefin or a neutral Lewis base that can be displaced by a monoolefin; and
T is hydrogen, hydrocarbyl or substituted hydrocarbyl, or may be taken together with L to form xcfx80-allyl group.
The polymerization processes described herein may be carried out in a batch or continuous mode of operation. The processes may be conducted as solution polymerizations, as non-solvent slurry type polymerizations, as slurry polymerizations using one or more of the olefins or other solvent as the polymerization medium, or in the gas phase. The catalyst employed may be unsupported or supported using a suitable catalyst support and methods known in the art. When the catalyst is in supported form, the supported catalyst may be used in slurry or gas phase polymerizations.
Examples of xe2x80x9csolid supportxe2x80x9d include inorganic oxide support materials such as talcs, silicas, titania, silica/chromia, silica/chromia/titania, silica/alumina, zirconia, aluminum phosphate gels, silanized silica, silica hydrogels, silica xerogels, silica aerogels, montmorillonite clay, and silica co-gels as well as organic solid supports such as polystyrene and functionalized polystyrene. See, for example, S. B. Roscoe et al., xe2x80x9cPolyolefin Spheres from Metallocenes Supported on Non-Interacting Polystyrene,xe2x80x9d Science, 1998, 280, 270-273.
The supported catalysts may be prepared by contacting the components of the catalyst system of the present invention with the support material, e.g, silica, for a sufficient period of time to generate the supported catalysts. The metal complex and the neutral Lewis acid, if used, may be added together, as a reaction product, to the solid support. Alternatively, the metal complex component may be added to a solid support which has been pre-treated with the neutral Lewis acid component.
Polymerization temperature and pressure have significant effects on copolymer structure, composition, and molecular weight. Suitable polymerization temperatures are preferably from about xe2x88x92100xc2x0 C. to about 200xc2x0 C., more preferably in the 20xc2x0 C. to 150xc2x0 C. range.
After the reaction has proceeded for a time sufficient to produce the desired polymers, the polymer can be recovered from the reaction mixture by routine methods of isolation and/or purification.
High molecular weight resins are readily processed using conventional extrusion, injection molding, compression molding, and vacuum forming techniques well known in the art. Useful articles made from them include films, fibers, bottles and other containers, sheeting, molded objects and the like.
Low molecular weight resins are useful, for example, as synthetic waxes and they may be used in various wax coatings or in emulsion form. They are also particularly useful in blends with ethylene/vinyl acetate or ethylene/methyl acrylate-type copolymers in paper coating or in adhesive applications.
Although not required, typical additives used in olefin or vinyl polymers may be used in the new homopolymers and copolymers of this invention. Typical additives include pigments, colorants, titanium dioxide, carbon black, antioxidants, stabilizers, slip agents, flame retarding agents, and the like. These additives and their use in polymer systems are known per se in the art.
Other features of the invention will become apparent in the following description of working examples, which have been provided for illustration of the invention and are not intended to be limiting thereof.